This invention relates to a novel 1-aryl-3-cyano-5-(het)arylalkylaminopyrazole derivative and a pesticide containing the same as an active ingredient, such as an agricultural and horticultural insecticide.
In the agricultural and horticultural field, a wide variety of insecticides have been developed and put to practical use for the purpose of controlling various harmful insects.
Pyrazole compounds known to have insecticidal activity include 5-(substituted)amino-3-cyano-1-phenylpyrazole derivatives disclosed in an unexamined published Japanese patent application 63-316771, 1-aryl-5-(het)arylmethylaminopyrazole derivatives disclosed in an unexamined published Japanese patent application 64-47768, and 1-aryl-3-cyano-5-(het)arylmethylideneiminopyrazole derivatives disclosed in an unexamined published Japanese patent application 5-148240.
However, these agricultural and horticultural insecticides are not necessarily satisfactory in all of insecticidal effect, insecticidal spectrum, safety, and the like.
Emergence of strains of harmful insects which have acquired resistance to the commercially available insecticides has now become a serious problem. For example, various insects having developed resistance to various types of pesticides (e.g., organophosphorus compounds), have come out in various sites of cultivation of vegetables, fruits, flowers, teas, wheat, rice, etc. Control of various pests caused by these insect pests is becoming increasingly difficult year by year, and development of a novel pesticide based on a unique skeleton has been awaited.
While there are some pesticides to which pathogens or insect pests have not yet acquired resistance, such as dithiocarbamate compounds and phthalimide compounds, they are not preferred from the viewpoint of environmental pollution because, in general, they should be applied in large amounts or frequently.
Accordingly, it has been keenly demanded to develop a novel pesticide which exhibits an excellent insecticidal effect, a broad insecticidal spectrum, and high safety with reduced influences on the environment.
An object of the present invention is to provide a novel pesticide which exhibits an excellent insecticidal effect, a broad insecticidal spectrum, and high safety with reduced influences on the environment. More specifically, it is an object of the invention to provide 1-aryl-3-cyano-5-(het)arylalkylaminopyrazole derivatives having the above usefulness and a process for synthesizing them efficiently.
As a result of extensive investigations, the inventor of the present invention has found that a novel pyrazole compound represented by the formula shown below is the compound that possesses the above-mentioned characteristics and thus completed the present invention. Thus, the gist of the invention lies in a 1-aryl-3-cyano-5-(het)arylalkylaminopyrazole derivative represented by the general formula (1): 
wherein R1 represents an alkyl group having 1 to 4 carbon atoms (hereinafter the carbon atom number will be expressed like xe2x80x9cC1-C4xe2x80x9d) or a C1-C8 haloalkyl group; R2 represents a hydrogen atom or a C1-C4 alkyl group; R3 represents an aryl or heteroaryl group which may be substituted with a substituent selected from a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C8 haloalkyl group, a C1-C4 alkoxy group, a phenoxy group which may be substituted, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 alkylsulfonyl group, a halogen atom, a nitro group, and a cyano group; and R4 represents a hydrogen atom, a C1-C4 alkyl group or a C1-C5 acyl group; X represents a nitrogen atom or a halogen-substituted carbon atom; and 1 and n each independently represent 0, 1 or 2; a process for producing the same; an intermediate for preparing the same, being represented by the following general formula (3): 
wherein R2, R3, R4, X, and 1 are as defined above; and use as a pesticide.
The present invention will be described in detail.
In the compounds represented by the general formula (1), R1 represents a C1-C4 straight-chain or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a t-butyl group; or a C1-C8 straight-chain or branched haloalkyl group, such as a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 2-chloroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group, a 3-chloropropyl group, a 3-bromopropyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2-dichloro-3,3,3-trifluoropropyl group, a 1,3-difluoro-2-propyl group, a 1,1,1,3,3,3-hexafluoro-2-propyl group, a 3,3,3-trichloropropyl group, a 4-chlorobutyl group, a 4,4,4-trifluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 5,5,5-trifluoropentyl group or a 6,6,6-trifluorohexyl group. Preferred of them is a C1-C4 alkyl group or a C1-C4 haloalkyl group.
R2 represents a hydrogen atom; or a C1-C4 straight-chain or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a t-butyl group. Preferred of them is a hydrogen atom.
R3 is an aryl group, such as a phenyl group or a naphthyl group, or a heteroaryl group having 3 to 8 carbon atoms and 1 to 3 hetero atom(s) arbitrarily selected from a nitrogen atom, an oxygen atom and a sulfur atom. These groups may be arbitrarily substituted with substituent R5 described below. Examples of them include: 
wherein R5 represents a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C8 haloalkyl group, a C1-C4 alkoxy group, a phenoxy group which may be substituted, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 alkylsulfonyl group, a halogen atom, a nitro group, or a cyano group; and m represents 0, 1 or 2.
Preferred of them are: 
wherein R5 and m are as defined above.
Still preferred are: 
wherein R6 represents a hydrogen atom, a hydroxyl group, a C1-C2 alkyl group, a C1-C2 alkoxy group, a C1-C2 haloalkoxy group, a C1-C2 alkylthio group, a halogen atom, a nitro group, or a cyano group.
R5 represents a hydrogen atom; a hydroxyl group; a C1-C4 straight-chain or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a t-butyl group; a C1-C8 straight-chain or branched haloalkyl group, such as a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 2-chloroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group, a 3-chloropropyl group, a 3-bromopropyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2-dichloro-3,3,3-trifluoropropyl group, 2,2-dichloro-3,3,3-trifluoropropyl group, a 1,3-difluoro-2-propyl group, a 1,1,1,3,3,3-hexafluoro-2-propyl group, a 3,3,3-trichloropropyl group, a 4-chlorobutyl group, a 4,4,4-trifluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, 5-chloropentyl group, or a 6,6,6-trifluorohexyl group; a C1-C4 straight-chain or branched alkoxy group, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, or a t-butoxy group; a phenoxy group which may be substituted with a C1-C4 alkoxy group or a C1-C4 alkyl group; a C1-C4 straight-chain or branched haloalkoxy group, such as a difluoromethoxy group, a trifluoromethoxy group, a 2-fluoroethoxy group, a 2-chloroethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,2-trichloroethoxy group, a 3-chloropropoxy group, a 3-bromopropoxy group, a 3,3,3-trifluoropropoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2,3,3,3-pentafluoropropoxy group, a 2,2-dichloro-3,3,3-trifluoropropoxy group, a 2,2-dichloro-3,3,3-trifluoropropoxy group, a 1,3-difluoro-2-propoxy group, a 1,1,1,3,3,3-hexafluoro-2-propoxy group, a 3,3,3-trichloropropoxy group, a 4-chlorobutoxy group, a 4,4,4-trifluorobutoxy group, or a 3,3,4,4,4-pentafluorobutoxy group; a C1-C4 straight-chain or branched alkylthio group, such as a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, or a t-butylthio group; a C1-C4 straight-chain or branched alkylsulfinyl group, such as a methylsulfinyl group, an ethylsulfinyl group, an n-propylsulfinyl group, an isopropylsulfinyl group, an n-butylsulfinyl group, an isobutylsulfinyl group, a sec-butylsulfinyl group, or a t-butylsulfinyl group; a C1-C4 straight-chain or branched alkylsulfonyl group, such as a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an isopropylsulfonyl group, an n-butylsulfonyl group, an isobutylsulfonyl group, a sec-butylsulfonyl group, or a t-butylsulfonyl group; a halogen atom; a nitro group; or a cyano group. Preferred of them are a hydrogen atom, a hydroxyl group, a C1-C4 straight-chain or branched alkyl group, a C1-C4 straight-chain or branched alkoxy group, a C1-C4 straight-chain or branched haloalkoxy group, a C1-C4 straight-chain or branched alkylthio group, a nitro group, or a cyano group.
R6 represents a hydrogen atom; a hydroxyl group; a methyl group or an ethyl group; a methoxy group or an ethoxy group; a C1-C2 haloalkoxy group, such as a difluoromethoxy group, a trifluoromethoxy group, a 2-fluoroethoxy group, a 2-chloroethoxy group, a 2,2,2-trifluoroethoxy group or a 2,2,2-trichloroethoxy group; a C1-C2 straight-chain or branched alkylthio group, such as a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, or a t-butylthio group; a halogen atom; a nitro group; or a cyano group.
R4 represents a hydrogen atom, a C1-C4 straight-chain or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a t-butyl group; or a C1-C5 straight-chain or branched acyl group, such as a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an isopropylcarbonyl group, an n-butylcarbonyl group, an isobutylcarbonyl group, a sec-butylcarbonyl group, or a t-butylcarbonyl group. Preferred of them are a hydrogen atom, a C1-C4 straight-chain alkyl group or a C1-C4 straight-chain acyl group.
Among the compounds of the present invention, preferred are those represented by the general formula (2): 
wherein R1 and n are as defined above; R7 represents 
R8 represents a C1-C2 alkoxy group, a C1-C2 haloalkoxy group, a C1-C2 alkylthio group, a nitro group or a cyano group; R9 represents a hydrogen atom, a hydroxyl group, a C1-C2 alkoxy group, a C1-C2 haloalkoxy group or a nitro group; and R10 represents a C1-C2 alkyl group.
Still preferred are the compounds in which R7 is 
In the above-described compound, the substituent R8 represents a methoxy group or an ethoxy group; a C1-C2 haloalkoxy group, such as a difluoromethoxy group, a trifluoromethoxy group, a 2-fluoroethoxy group, a 2-chloroethoxy group, a 2,2,2-trifluoroethoxy group or a 2,2,2-trichloroethoxy group; a methylthio group or an ethylthio group; a nitro group; or a cyano group.
R9 represents a hydrogen atom; a hydroxyl group; a C1-C2 haloalkoxy group, such as a difluoromethoxy group, a trifluoromethoxy group, a 2-fluoroethoxy group, a 2-chloroethoxy group, a 2,2,2-trifluoroethoxy group or a 2,2,2-trichloroethoxy group; or a nitro group.
R10 represents a methyl group or an ethyl group.
The compounds represented by the general formula (1) are prepared, for example, in accordance with the following reaction schemes 1 to 3:

wherein R1, R2, R3, X, 1, and n are as defined above; Y represents a halogen atom, a hydroxyl group or a salt thereof, or a dialkylamino group; and Z represents a releasable group, such as a halogen atom, a hydroxyl group, etc.
The process of reaction scheme 1 is characterized in that S(O)nR1 is introduced into the compound of the general formula (3).
This reaction is carried out by allowing R1S(O)nxe2x80x94Y (wherein Y and n are as defined above) to react on the compound of the general formula (3) in a solvent in the presence of, if desired, a base at 0xc2x0 to 150xc2x0 C., preferably 0 to 100xc2x0 C. Bases useful in the reaction include the tosylate of an amine compound, e.g., dimethylamine or pyridine, and commonly used inorganic bases such as alkali metal carbonates. The base is used in an amount of 0.5 to 2.0 molar equivalents, preferably 0.8 to 1.5 molar equivalents to the compound (3xe2x80x2).
Solvents useful in the reaction include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as chloroform and methylene chloride; and polar solvents such as tetrahydrofuran and N,N-dimethylformamide.
According to necessity, R4 is introduced to the nitrogen atom either before or after the above reaction. For example, the compound (3) is obtained by allowing R4Z (wherein Z represents a releasable group, e.g., a halogen atom, a hydroxyl group, etc.) to react on the compound (3xe2x80x2) or an alkali metal derivative thereof in a solvent in the presence or absence of a base at 0xc2x0 to 150xc2x0 C. Solvents useful in this reaction include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as chloroform and methylene chloride; tetrahydrofuran, and N,N-dimethylformamide.
Bases useful in this reaction include organic bases such as pyridine and triethylamine and alkali metal carbonates.
The compound represented by the general formula (3) is prepared by, for example, according to the following reaction schemes 4 to 7.

The process of reaction scheme 2 is characterized in that the compound of the general formula (5) is reduced with a reducing agent.
The reaction is carried out by adding 0.2 to 5.0 molar equivalents, preferably 0.25 to 2.0 molar equivalents of a reducing agent to the compound of the general formula (5) in the presence or absence of a solvent and allowing them to react at xe2x88x9220xc2x0 to 150xc2x0 C., preferably 0xc2x0 to 120xc2x0 C.
The reducing agent used for the reaction includes sodium borohydride, sodium cyanoborohydride, lithium borohydride, and lithium aluminum hydride.
The solvent used includes polar solvents such as ethers, e.g., diethyl ether, dioxane, and tetrahydrofuran, and alcohols, e.g., methanol, ethanol, and propanol.
The compound represented by the general formula (5) can be prepared by, for example, in accordance with the process described in an unexamined published Japanese patent application 5-148240.
The process of reaction scheme 3 is characterized in that the compound of the general formula (6) is (het)arylalkylated. In the scheme Z represents a releasable group such as a halogen atom and a hydroxyl group.
The reaction is carried out by allowing the compound (6) or an alkali metal derivative thereof and R3R2CHZ (wherein R2, R3, and Z are as defined above) to react in a solvent in the presence of, if desired, a base at 0xc2x0 to 150xc2x0 C. The solvent useful in this reaction includes aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as chloroform and methylene chloride; tetrahydrofuran, and N,N-dimethylformamide.
The base used in the reaction includes organic bases such as pyridine and triethylamine and alkali metal carbonates.
The compounds represented by the general formula (1) according to the present invention are useful in agriculture, horticulture and in the fields relating to housekeeping, cattle, and pets as controlling agents on pests such as arthropods (especially mites and insects), nematodes, worms and protozoa. Specifically the compounds have high controlling activities on eggs and larvae of Hemiptera, such as Delphacidae (e.g., Sogatella furcifera, Nilaparvata lugens, and Laodelphax striatellus), Deltocephalidae (e.g., Nephotettix cincticeps and Tettigella viridis), and Aphididae (e.g., Myzus persicae); Lepidoptera, such as Spodoptera litura, Chilo suppressalis, Cuapha locrocis medinalis, and Plutella xylostella; Coleoptera, such as Callosobruchus chinensis; Diptera, such as Musca domestica, Aedes aegypti, and Culex pipiens pallens; and Orthoptera, and are therefore useful as an active ingredient of agricultural and horticultural insecticides. The insects which are controllable by the compounds of the present invention are not limited to these examples.
In using the compounds of the invention as agricultural and horticultural insecticides, they may be used alone but are preferably formulated into compositions together with adjuvants customarily employed in the art. While not limiting, the forms of the agricultural and horticultural insecticides include emulsifiable concentrates, wettable powders, dusts, flowables, powders, granules, tablets, oils, sprays, and fumigants. These preparations can comprise one or more than one compounds of the invention as an active ingredient(s).
The adjuvants are used in the agricultural and horticultural insecticidal preparations for the purpose of improvement of the insecticidal effect, stabilization of the preparations, improvement of dispersibility, and the like. Useful adjuvants include carriers (diluents), spreaders, emulsifiers, wetting agents, dispersants, and disintegrants. Suitable liquid carriers include water; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, butanol and glycol; ketones such as acetone; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; methylnaphthalene; cyclohexane; animal or vegetable oils; and fatty acids. Examples of suitable solid carriers are clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, and gum arabic. General surface active agents serve as an emulsifier or a dispersant. For example, anionic, cationic, nonionic or amphoteric surface active agents, such as sodium higher alcohol sulfates, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ethers, and lauryl betaine, are useful. Further, spreaders, such as polyoxyethylene nonylphenyl ether and polyoxyethylene laurylphenyl ether; wetting agents such as dialkyl sulfosuccinates; fixing agents, such as carboxymethyl cellulose and polyvinyl alcohol; and disintegrants, such as sodium lignin sulfonate and sodium laurylsulfate can be used.
The concentration of the active ingredient in the agricultural and horticultural insecticides is selected from the range of from 0.1 to 99.5%, being appropriately decided in accordance with various conditions such as the form of the preparation and the method of application. For example, a suitable active ingredient concentration is about 0.5 to 20% by weight, preferably 1 to 10% by weight, in dusts; about 1 to 90% by weight, preferably 10 to 80% by weight, in wettable powders; or about 1 to 90% by weight, preferably 10 to 40% by weight, in emulsifiable concentrates.
Emulsifiable concentrates are prepared by mixing the compound of the invention as an active ingredient with a solvent, a surface active agent, etc. The emulsifiable concentrate is diluted to a prescribed concentration on use. Wettable powders are prepared by mixing the active ingredient with a solid carrier, a surface active agent, etc. The wettable powder can be applied as diluted to a prescribed concentration. Dusts are prepared by mixing the active ingredient with a solid carrier, etc. and can be applied as such. Granules are prepared by mixing the active ingredient with a solid carrier, a surface active agent, etc., followed by granulation. Granules can be applied as such. The above description about the methods for preparing the above-described compositions of various forms is not intended to limit the invention, and one skilled in the art can select an appropriate method in accordance with the active ingredient and the purpose of application.
The agricultural and horticultural insecticide of the invention comprising the compound of the invention as an active ingredient can further contain optional active ingredients, such as other bactericides, insecticides, miticides, herbicides, insect growth regulators, fertilizers, soil conditioners, and so on.
The usage of the agricultural and horticultural insecticide according to the invention is not particularly restricted, and it can be used for foliar spray treatment, submerged application, pre-emergence soil treatment, seed treatment, and the like.
For foliar spray treatment, a solution having a concentration of 5 to 1000 ppm, preferably 10 to 500 ppm, is applied in an amount of about 100 to 200 l per 10 are. For submerged application, granules having an active ingredient content of 5 to 15% is scattered in an amount of 1 to 10 kg per 10 are. For soil treatment, a solution having a concentration of 5 to 1000 ppm is applied in an amount of about 1 to 10 l per m2. For seed treatment, a solution having a concentration of 10 to 1000 ppm is applied in an amount of about 10 to 100 ml per kg of seeds.
The usage of the insecticide for cattle or pets according to the invention is not particularly restricted. The preparation can be applied in any manner, for example, by applying to a pet""s collar or dusting cattle.